Extreme pressure lubricant



Patented Feb. 17, 1953 EXTREME PRESSURE LUBRICANT David E. Adelson and George L. Perry, Berkeley,

and George G. Prit'zker, Sausalito, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing.

Application February 4, 1950, Serial No. 142,536

12 Claims. (Cl. 252---46.7)

' This invention rel-ates to extreme pressure lubricants capable of withstanding high pressures at elevated temperatures under severe and adverse operating conditions. More specifically this invention pertains to improvement of extreme pressure lubricants by enhancing their extreme pressure properties and at the same time rendering them substantially non-corrosive and stable, by addition of a novel additive thereto, in relatively minor amounts.

Natural and/or synthetic lubricants per so are not capable of withstanding extreme pressures at high temperatures, high speeds and under severe loading conditions as generally encountered in present-day lubricating such as internal combustion engines of various ty es, transmission devices, certain types of gears, e. g. hypoid gears, metal fabrication such as in cutting and drawing and the like. Under such conditions of lubrication, the protective film formed between contactr ing surfaces, by the lubricant, so as to prevent direct metal-to-metal contact, breaks down or ruptures and seizure or even welding of metal parts occurs, resulting in serious damage to the elements being lubricated. serious, weakness generally inherent in undoped lubricants, extreme pressure agents are added which formprotective films between contacting T overcome this surfaces and which possess among their properv ties the function of imparting film strength and '1 oiliness to lubricants, thus preventing their breakdown and rupture under the ab0ve-de scribed lubricating conditions.

The action of extreme pressure agents is largely a physiochemical phenomenon and this accounts primarily for their effectiveness as extreme pres sure agents. These agents or materials, in addition to increasing the film strength of lubricants, become reactive with contacting surfaces forming thereon an alloying protective coating or film of great strength and thermal stability. This tenaioiously adhering adsorbed protective film not only reduces friction between relatively moving parts suohas encountered in internal combustion around about 150 C. and higher, the performance of a given lubricant must depend upon its composition, the composition of the contacting surface being lubricated, as well as the conditions to which the combination is subjected.

Although extreme pressure additives to be effective should be reactive with contacting surfaces, this reactivity should not be corrosive to the reactive surface. This is generally a serious draw-back of known extreme pressure agents, for serious damage to metal surfaces, particularly such as alloy bearings and the like, might result. Such additive should also not tend to promote oxidation which generally prompts formation of corrosive acidic materials, sludge, lacquer and varnish which results in sticking and fouling of movable engine parts and the like.

Numerous compounds and mixtures of compounds have been proposed and tried as extreme pressure agents for lubricants, the best of which have only moderately improved the extreme pressure properties of the lubricant and generally at the expense of increased corrosiveness and instability of the lubricant. Among such compounds may be mentioned organic oxygen-containing compounds such as fatty acids, esters, ketones, oxidized petroleum fractions; organic compounds containing sulfur or oxygen and S111- fur such as sulfurized fatty oils, acids, etc.; organic corn-pounds containing chlorine usually obtained by chlorinating organic compounds :or petroleum fractions; organic compounds containing phosphorus; organic compounds containing lead and especially such compounds when in conjunction with an active sulfur compound.

Of the general classes of extreme pressure compounds enumerated, sulfur and/or halogenoontaining com-pounds appear to be most effective and are therefore preferred. However, these have serious defectsin that most sulfur compounds to be effective must contain a major amount of sulfur in an active statewhich is highly corrosive and. has a tendency to separate out and form sludge. Materials of this type, when in combination with halogen-containing compounds, have a deleterious effect by liberating highly corrosive acids from the halogenated compounds and also interfere with their function as an extreme pressure dope. Halogen-containing compounds when used alone, become highly corrosive to alloy metals such as cadmium-silver, copper-lead, etc.,

so as to render them useless after short periods of use.

It is an object of the present invention to .provide an improved extreme pressure type lubricant capable of effective lubrication under high pressures at elevated temperatures and adverse operating conditions. Still another object of this invention is to provide an improved, stable, sludgefree, non-corrosive extreme pressure lubricant. Also, it is an object of this invention to provide an improved extreme pressure lubricant by addition to any lubricating carrier or base a minor amount of a novel reaction product of this invention. Still another object is to form an improved non-corroshre-extreme pressure additive from the: reaction products of" this invention.

Other objects of this invention .Will appear as thev description proceeds.

To the accomplishment of the foregoing and.

related ends, this invention consists of features which will be hereinafter fully described andparticularly pointed out in the claims, the-follow,- ing description setting forth in detail: certain embodiments of the invention, these-being illustrative of but a few variations in which the. principle of the invention may be employed.

Broadly stated, this invention is directed tov the use in liquid hydrocarbon compositions such as lubricants, fuels, greases, rust-inhibiting; compositions and the like, as well as synthetic lubricatingbases, of: a reaction productobt-ained taining: at least;;0ne XR;radical, whichcompound can be representedqby theegeneralformula:

wherein-A- is .an .organic;radical selectedfrom the class ,consistingof aliphatic, cycloaliph-atic,

aromatic ;-and heterocyclic organic radicals; n .is

an :integer j of at :least 2.;a-ndrj-represents the numberof acidic radicalsrQ which -areqattachedto A one: of the; acid; radicals represented by a- -C iXR radical andthe other; acid radicals represented by-Q canrbe th'eisame as CXXR or: may be: selectedfrom1 oxy inorganic acids such as sulfonic; sulfinic; nitric and; acids of phosphorus; 'X.,is antelement-selected from the group; consistingofO,'- S=, Se and: Te and 'inithe radical-(IXXRthe Xscanjoezthe sameor different? R; can be hydrogen, alkyl, cycloalkyl, aralk-yl alkylaryl', aryl radicals ora cationic portionof :a molecule such asNaiLi, Ca Ba; Sr, Sn; Ni, A1,Zn, P1) or organic amines, at :least-one of the-Rs either the acid .or polar radical XR beingrhydrogen; Y is-apol-ar selected from the group consisting of'nitro, nitroso, amino, sulfo and-halo groups; m'isan' integerof-at least l" 'andpreferably l'to 3;"and p can be a .whole number varying from zero to one.

Specific compounds which are-embraced within thescope offthe above-general formula and 51 of *Which anyand all as well as :mixtures :thereof canzbe used to form the reaction products of thisinventioninclude: hydroxy'malonic acid, hydroxy succinic=acid, tartaric acid, octyl tartaric acid; citric-acid, hydroxy glut-aric acid, hy-

droxy= adipic acid, chloromalic" acid, mercapto' B,-sulfenicu acid ofw-hydroxy decyl carboxylic acid Na salt of;B-sulfonic-;acid-of w-hydroxyl hexyl carboxyliclacid naphthol 3-.-carboxylic 6-' 4 sulfon-icacid; etc. Any of: these acidszcan be partially esterifiedto form partial esters, which partial esters can be used to form the condensation reaction product of this invention. Esters/which are particularly preferred to form condensation reaction products of this invention include acid ester of oleyl malate, acid ester of "oleyl tartarate, acid ester of oleyl citrate, acid ester'of-ste'aryl citrate, acid ester of cetyl citrate, 9,10 octa-decenyl acid citrate, dodecyl acid, hydroxy succinate, oc-tyl mercapto acid phthalate, acid ester of methylene disalicylate, dihydroxy dithiomonostearate of butyl alcohol, acid ester of oleyl dihydroxyl thiophene carboxylate, B-sulfonic acid of oleyl w-hydroxyl decanate; etc: In: addition; theifullestersran be -used-to form'condensation products of this,

invention, among: which can be: mentioned: dioleyltartarate, dioctyl tartarate, dibenzyl tartarate; di'phenyl; tartarate, dioleyl. malate; trioleylcitrate; dioleyl ester of methylene salicylic acid,:.distearyl esterof-methylene salicylic acid,

dioleyl ester-of propyl dihydroxy thiophene dicarboxylic acid, etc. mixtures thereof can be partially neutralized with -a metal compound or organic bases to form salts; which salts can be used to form condensation products'ofth-is invention: Preferredexamples of such saltsare sodium salt" ofacid ester of oleyl'malate, sodium-or potassium salt of'acidtesterof oleyl tartarate, calcium saltof acid ester of oleyl citrate, calciumsalt of methyl ene' disalicylate, triethanolamine salt of acid ester of stearyl" citrate, dibutyla-mine "salt of acid ester 'ofioctyl 'tartarate, etc. If 'desired, the saltsof thisinvention can' be produced after the condensation products of thisinvent-ion haveb'een formed.

The above polar-substituted organie-polyacidic compounds, their ester and/or-salts are'reacted with'alkylene oxide, sulfide-and/or-imine to form the desired condensation reaction product of this invention; The alkyleneoxides which can be-- used are:- ethyleneoxide, propylene oxide; butylene oxide, amylene oxide, epichlorhydrin, glycide, alkyl glycides, glycidyl compounds, e. g:, glycidyl isopropyl ether, and the like; Instead of the alkylene oxides as enumeratedabove; ,the'

Sulfide andimine analogues can be used,v of which particularly preferred areethylene sulfide, propylene sulfide, ethylene imine; propylene W imine and the like.

The mole ratio of the 'alkylene oxide, sulfide or.

imine to the polar-containing organic polyacidic compound canvary over wide limits in order to produce the desired reaction product. The pre-'- ferred'ratio of oxide-to the'polyacidic organic compound or itsderivative, is 4:1 to 12:1, respectively. varied over wide'dimits and primarily depends upon the reacants-used in .forming the condensation product of-thi-sinvention. Broadly, the reaction temperature lies between.50 C. and 350"CL, and generally the reaction temperature lies between 75C. and200 C. The reaction can be carried out underpressure in.-a, suitable reaction vessel, with thepressure varying from 50-pound gauge pressure to over LOGO-pound gauge pressure. The, condensation reaction, however, need not be-carried out under pressure, but it is preferredthat it be carried out in an enclosed "vessel. Catalysts may be used in carryingout the condensation reaction, and the catalyst may be either acid or basic. A few examples of'such-cat-alystg areboric acid, caustic The acids or the esters or The reaction temperature can. be-

alkalies, alkali alcoholates, e. g., sodium methylate, sodium ethylate; sodium oleate, di-sodium phosphate, sodium di-hydrogen phosphate, organic amines, e. g., ethylene diamine, etc. The reaction can be carried out in a suitable solvent or diluent. The diluents can be light or heavy hydrocarbons such as benzene, kerosene, gas oil, mineral oil or dioxane (purified by distillation with alkylene reagents), or any other suitable organic diluent which is substantially non-reactive with the constituents comprising the condensation reaction product of this invention and from which products of this invention can be easily removed. One method of preparing lubricants of this invention is to form the condensation reaction product directly in the base lubricant such as a mineral lubricating oil, alkylated napthalene, and the like; filtering and purifying the compounded lubricant, if necessary, and using said compounded lubricant for its intended purpose. r

The mechanism of the present invention is complex. ucts form in which the alkylene oxide, sulfide or. imine attaches to both the carboxyl and hydroxyl radicals, provided both are free, although the reaction can be controlled so that only the carboxyl or hydroxyl groups are attacked. In view of the complexity of the reaction,it is desired to cover within the scope of the present invention all possible condensation products and mixtures thereof which are formed from reaction products of this invention.

The reaction is carried out under conditions.

of this invention are carried out is their solubility in base lubricants. Products which are too highly condensed tend to lose their oil solubility, which can be overcome, however, by addition or use of oil solubilizers.

Broadly stated, the method of preparing condensation reaction products of this invention can be accomplished by employing the following procedure. About one mole of an organic polarcontaining polycarboxylic acid or derivative thereof such as tartaric acid, oleyl tar'tarate, acidv ester of methylene disalicyclic acid, etc., is slowly heated in a suitable reaction vessel, such as an autoclave, and the product heated to above about 75 C. and higher, depending upon the organic polyacidic material used. The material can be I heated per se or dispersed in a diluent su'ch as mineral oil and heated therein. To the heated mixture is then added from 1 to and generally 2, to 12 moles of an alkylene oxide, sulfide or imine and the reaction allowed to proceed, varying the reaction temperature by either cooling or heating above the. temperature indicated above, in order to form a smooth reaction, and the ingredient allowed to react for from 4 to 48 hours. The reaction is preferably carried out under pressure and in the presence of a basic catalyst and is regarded as being completed when the average molecular weight of the organic polyacidic starting material has increased by at least 44 weight units and higher.

Generally, mixtures of condensation prod- To more clearly illustrate the present invention, 7

Example I Approximately 1 mole of tartaric, acid was slowly heated to a temperature between C.'

and C. with constant stirring and about 2 to 8 moles of ethylene oxide was slowly added together with a catalytic amount of sodium methylate and the mixture was allowed to react under pressure for 48 hours at the above temperature. At the end of the reaction period, the tartaric acid indicated an increase in average molecular weight between 90 and weight units. The condensation product when added to mineral oil in minor amounts imparted extreme pressure properties to the oil.

Enample II Approximately 1 mole of tartaric acid was dispersed in purified dioxane and between 2 and 10 moles of ethylene oxide was added slowly and the mixture reacted under pressure at between 75 and 100 C. in the presence of ethylene diamine catalyst for about 48 hours. At the end of the reaction period, the condensation product was removed from the dioxane and the acid indicated an average increase in molecular weight between 360 and 450 weight units. The condensation product when added to mineral oil imparted extreme pressure properties to said oil'.

Example III Following the procedure and'conditions as outlined in Example II, malic acid was reacted with ethylene oxide. The condensation product thus formed had good extreme pressure properties.

Example IV Approximately 1 mole of hydroxy glutamic acid was reacted with 4 to 10 moles of propylene oxide under conditions set forth in Example I. At the end of the reaction period, the hydroxy .glutamic acid indicated an average increase in molecular weight between 348 and 580 weight units. The condensation product when added to an oil imparted extreme pressure properties thereto.

Example V Approximately 1 mole of z-propyl dihydroxythiophene 3-4 dicarboxylic acid was reacted with 5 to 15 moles of ethylene oxide in the presence of sodium methylate in purified dioxane at be.- tween 100 and C. for about 48 hours. At the end of the reaction, the condensation product was removed from the solvent and on analysis indicated an increase in average molecular weight over the acid of from 220 to 660 weight units.

. Example VII 1 Approximately 1 mole of tartaric acid was reacted with 4 to 10 moles of ethylene sulfide under conditions set forth in Example II. On analysis, the tartaric acid indicated an average molecular weight increase between 240 and 600 weight units. The condensation product was soluble in oil.

7. ExamplezzVIII Malic: acid was used in .=.place" off tartaric'ra'cid to form .a condensationproduct as set: forth in Example VII. The sulfur-containing condensation productwhen added to oil imparted extreme pressure properties toit. On' analysis, the malic acid-indicated an average molecular'weightincrease between 240 and600Weight units.

Example. IX

Approximately 1 mole of tartaric acid' was heated with 4 to moles ethyleneimine under conditions as set forth in Example WI on analysis, the tartaric acid indicated an increase in molecular weight between .168 and 420 weight units. The nitrogen-containing condensation productwas oil-soluble and possesses good antioxidant properties.

Eatample X.

Approximately 1 mole ofa'cid' ester of oleyl malate. wasdispersed in purified dioxane and between 4 and moles ofethylene oxide'were slowly added and the mixture reacted between and 125 C. in the presence of sodium methylate forabout 48 hours. At the end of the reaction period,.the condensation product was removed and the acid ester indicated an average increase in molecular weight between 1'76 and 440 weight units. The condensation product whenadded to oil imparted extreme pressure properties;

Example XI Following the procedure of Example X, ap-

proximately 1 mole of octyl mercapto acid phthalate and 4 to 15 moles of ethylene oxide werereacted under conditions set forth in Example but the reaction .temperature' being maintained at above C. The esterzindicated an average increase in molecular weight between 132 f and :352 weight units.

Example XII Approximately 1 mole of dibenzyl tartarate and between 2 and 10 moles of amylene oxide were reacted under-conditions set forth in Example .X, while maintaining the reaction temperature above C. increase in molecular-weight between 175 and 345' weight units.

Example XIII Approximately :1 mole of Jdihydroxydithiobutyl monostearate was reacted, with.4 .to.110.moles1of ethylene sulfide under conditions set forth. in Example X. The ester-indicated an average increase-in molecular.weight of around 2.40 weight units... The condensationproduct.contained. a substantiallincreasein sulfur content and.the product possessed good extreme pressure proper-- ties.

Example XIV Approximately 1 mole of dioleyl malatewas dispersed in purified dioxane andb'etween'4 and 12' moles of ethylene oxide added and themixture slowly reacted in.the.presence of sodium methylate at between 75 and'125 C. for about 48 ihours. At the end of the reaction period, the condensation product was recovered "and the ester indicated an average increase in molecular weight between 176 and 440 weight units. The condensation product'wasoil soluble-and im parted extreme pressure properties to the "oil.

The ester indicated an average EmamplaXl/T Followingtheprocedure setforth in Example XIV. but-using 'glycidyl isopropyl ether, thecondensation product formed indicated that the ester" increased in average molecular weight b'y about"1,000 weight units:

ExampleXVI.

Approximately 1" mole of tartaric acid was dis persed'in purified dioxane and between 4 and 12 moles of ethylene oxide added and the mixture slowly reacted in the presence of 'sodium methyl-- ate-at'between 75 'and 125 "C. for about '48 hours: At'th'e end of the'reaction'period, the condensationproduct'was recovered and the ester indicated an average increase in molecular weight between 176"and'440' weight units. The condensation product was oil soluble and imparted extreme pressure properties to the oil.'.

Example XVII Followingthe;procedure :set forth in Example XIV. but using ethylene sulfide," the: condensation productiformed containedtsubstantial amount-of sulfur; and the i ester: indicated an average increaselin molecular.- weight ofover 240.-weight units}.

Example XVIII Following; the procedureset forth in'Example XIV butusing ethylene imine, the condensation product formed contained substantial amount of nitrogen and the "ester indicated an average in-. crease in molecular weight of over 168 weight units;

Example XIX Acondensationproduct was. prepared by reacting potassium. salt: ofv acid ester: of oleyl tartarate with ethyleneoxide underthe reaction condition setforth in ExampleXEV; The product obtained indicated .an .average molecular weight increase overthesalt of around 220 weight units.

Example XX A..condensation product was preparedby reacting calcium. methylene disalicylate with .eth-. ylene oxide. under. conditions set forth .in ExamplaXIV. except.that. the reaction. temperature wasincreasedto. to 200? C.. The product Ob:- tainedl indicated an average molecular. weight increaseoverv the salt ofaround 900 weight units.

Emample XXI Approximately" 1 mole of B-sulfonic acid of w-hydroxyjdecyl carboxylic acidwas dispersedin 7 purified dioxane and between .4 and 12 moles of ethylene oxide added andthe'mixtureslowly re acted in-the presence of sodium methylate at between:.7'5 and125C. forabout 48 hours. At the endof the reactionperiod, the condensation product was: recovered and the ester indicated anaverage increase in molecular weight between 176 and 440 weight units. The condensation product was oil soluble and imparted extreme pressure properties to the oil.

Condensation reaction products of this invention can be halogenated and/or sulfurized, sulfophosphorized, phosphorized and the like with such reagents as chlorine, sulfur; sulfur chloride; inorganic polysulfides, e. g.', sodium polysulfide: phosphorus sulfide such as PzSs, P4S3; phosphorus oxides," e: g.', P205; phosphorus oxychlorides, e: gFPOCls, elemental phosphorus and the like.

Emample :XXII

About 1 mole of the condensationproduct 'of 9 Example XIV and 4 to 8 moles of PzSs were reacted at 125 to 250 C. for about 24 hours. The phosphorized-sulfurized condensation product was extracted with a ketone and the solvent thereafter removed. On analysis, the product indicated the presence of reacted sulfur and phosphorus in the molecule.

Example XXIII About 1 mole of the condensation product of Example XIV and 4 moles of sulfur were reacted atabout 160 C. for about 24 hours. The sulfurizedproduct was isolated by means of toluene to yield a product containing sulfur in the molecule. Any of the above condensation products can be admixed with from 1 to 8 parts of the acid or acid'ester from which the condensation products are derived. Thus, for example, one part of the condensation product of Example II when admixed with four parts of tartaric acid and the mixture added to a base mineral oil the resultant composition (A) possesses excellent extreme pressure properties.

Base lubricants which may be improved by addition of minor amounts of condensation re- 1' action products of this invention may be selected from a wide variety of natural oils such as mineral oil, vegetable oil, animal oil, marine oil and mixtures thereof. In addition, synthetic lubricants may be used such as polymerized olefins, organic esters, e. g., 2-ethylhexyl sebaeate, dioctyl phthalate, trioctyl phosphate, silicon polymers, e. g., dimethyl silicone polymer; mixtures of natural and synthetic lubricants; lubrieating emulsion bases and the like. General formulation of compositions of invention can be'represented by:

Amount (percent by weight) Brimary additive: Condensation reaction product of this invention 0.01 to 10% Secondary additive: Detergents,

e. g., sulfonates, solubilizers, e, g., esters of polyhydric acids (sorbitan monooleate, glycerol monooleate, etc.), corrosion inhibitors, etc. to 2% l (0.01 to 1%) Base: Nature oil such as mineral oil and/or fixed oils and derivatives thereof and/or synthetic lubricants Balance The following table, illustrates compositions of this invention:

Compositions of this invention were evaluated for their extreme pressure properties on a spurgear machine, which essentially consists of two geometrically similar pairs of gears connected by two parallel shafts. The gear pairs are placed in separate gear boxes, which also contain the suporting ball bearings. One of the shafts con sists of two sections connected by a coupling. Loading is accomplished by locking one side of the coupling and applying torque to the other. The conditions of the test were:

Speed: 7100 R. P. M. Test duration: mins. running at each load Specimen: involute spur gear (SAE 3312 steel) Composition: Score load (lbs.)

Mineral oil 5 Mineral oil containing 1% sorbitol 25 Mineral oil containing 1% sorbitan monooleate g 25 Mineral oil containing 2% salicylic acid 20 Mineral oil containing 5% polyethylene oxide polymer (M. W. 1500) Mineral oil containing 1% methylene disalicylic acid lVlZineral oil containing 1% glycerol monooleate Composition 3 (as in table) 70+ Composition 4 (as in table) 70+ Composition 1 (as in table) 70+ Composition 2 (as in table) 70+ Composition 6 (as in table) 70+ Composition 7 (as in table) Composition 13 (as in table) Composition 17 (as in table) Composition A 75+ Because of its synergistic effect the reaction product of this invention can be combined with other additives in lubricants, such as blooming agents, pour point depressants or viscosity improvers, extreme pressure agents, antifoaming agents and the like. Among the specific additives which can be used are oil-soluble detergents which include oil-solube salts of various bases with detergent forming acids. Such bases include metal as well as organic bases. Metallic bases include those of the alkali metals and of Cu, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases as primary, secondary and tertiary amines and quaternary ammonium bases.

Examples of detergent forming acids are the various fatty acids of, say, 10 to 30 carbon atoms, wool fat acids, paraffin wax acids (produced by oxidation of paraffin wax), chlorinated fatty Compositions Components Composition of Ex. Composition of Ex. Composition of Ex.

Composition of Ex. Composition of Ex. Composition of Ex. X Composition of Ex. Composition of Ex. Composition of Ex. Ca petroleum sulfonate Sorbitan monooleate Sorbitol monooleate Glycerol monooleate High molecular wt. aliphatic am Mineral oil Mineral oil alkyl naphthalene..." Dimethyl silicone fluid 1 The additives were present in amounts varying from 0.5 to to 5%.

acids, rosin acids, aromatic carboxylic' acids J including aromatic fatty acids, aromatic hydroxy fatty acids, paraflin'wax benzoic acids, various alkyl salicylic "acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkyl-phenol) sulfides and disulfides, methylene bis alkyl phenols; sulfonic acids such'as' may be produced by treatment of alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid; sulfuric acid monoester's; phosphoric, arsonic and antimony 'acid mono and diesters, including thecorresponding thiophosphoric, arsenic-and antimony acids,-phosphonic and arsonic acids and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thio'ph'o'sphate diester the alkaline earthdiphenolates, specifically'the calcium and barium'saltsof diphenol mono and p'olysulfides.

'Non m etallic detergents include coinpounds such "as r the ph-osphatides, P such -a-s lecithin and cephalin; certain fatty oils-as rapeseed oils, oltolized fattyor mineral oils and thelike.

Anexcellent metallic detergent for the present purpose inthe calcium salt-of OiY-Soluble petroleum sulfonic' acids. This mayloc -present advantag'e'o'usly in* the amount of about 0.025% to "0.2% sulfate-ash, 'Also-alkaline -rrietal "salts of alkyl phenol-aldehyde condensation reaction p-roductsare excellent detergents.

Antioxidants-comprise several'-types, for example; alkyl phenols such as 2 ,4,6 tr'i'methylphenol, pentamethyl phenol, YZA-d-imethyI-G-tertiarybutyl phenol, '2 i4 -dimethyl-fi-oc'tyl phenol, 2,6 ditertiary-butyl=4-methyl phenol, -'2,4,6-tritertiary-butyl phenol and the like ;aminc phenols asbenzyl amino phenols z-amines such asdibutylphenylene dia-mine, diphenyl amine, phenylbeta naphthylamine, :phenyl-alpha-naphthylamine; dinaphthyl amine.

1 Corrosion inhibitors or anti-rustingcompouhds may-also bezpresent; such-as d-icarboxyiic acids of '16- and more carbon atoms; alkali-metal and alkaline earth salts of sulfonic -acids -and "fatty acids; =organic compounds containing an acidic radical-in close proximity toa nitrile, nitro or -nitroso group (e gs-alpha cyano stearic acid).

Extreme..-pressure agents which may be used comprise:'--'esters of. phosphorus acids such as triary-l, =a'lkyl hydroxyaryl, or aralkyl phosphates, thiophosphates or phosphites and the like; neutral-aromatic sulfur compounds of relatively hi'gh boilin'g temperatures such as diaryl sulfides, d-iaryl clisulfides-alkyL-aryl disulfides, e. .g. diphenylsulfidadiphenol sulfide, dicresol sulfide, =dixylenol sulfide,- methyl butyl 'diphenol sulfide, dibenzyl sulfide, corresponding diand tri-sulfides, and the like; sulfurized fatty oils' or esters of fatty acids and monohydric alcohols, e. g. sperm oil,.-jjoba oil, etc.; in whichthe sulfur is strongly bonded; sulfurized long chain olefins such as may be obtained by dehydrogenation or cracking of wax; sulfurized 'phosphorized fatty oils or acids, phosphorus acid esters having sulfurized organic radicals,'such as esters of phosphoric or phosphorus acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons, such as chlorinated paraffin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc.; or

chlorinated esters of fatty acids containing the chlorine in position other than alpha position.

Additional ingredients may compriseoil-soluble urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides,"carbazones;etc.; polyisobutylene polymers, unsaturated polymerized 1'2 esters of fatty acidsandmonohydric-alcohols and other :high molecular weight *oil soluble compounds.

Depending uponthe additive used and conditions under which it is used, the amount of additive used may vary from 0.1to 2%or higher.

The novel reactionaproductsof this invention, in addition to being excellent lubricating oil improving agents, are potent oxidation inhibitors for fu'els,-' natural and-synthetic rubber, wax coatingc'ompositions and other or'ganic materials.

-It is to be un'dersto'od that while theifeatures of 'the invention have be'en describe'd and illustratedin connection with certain specific 'ex-' amples, the invention, however, is not to be limited thereto or otherwise restricted, except by the" prior art and thebroad'scope of thedisclosed invention.

' The invention claimed is:

-1. A lubricating composition comprising a major amountof a liquid organiclubricating base having incorporated therein from about 0.01 to 10% of reaction productobtained by reacting an aliphatic compound selected from-thegroup consisting'of C2-C5 alkylene oxide, C2'C5 alkylene sulfide, andzC -alkylene imine' 'withan organicpolyacidic compouncl containing: from 1 -to'3 freecarboxylicacid groups and-at least one hydroxy' group, said reaction being carried out at atemperatu're -'of:at-' least"7-5 C. in the mole ratio of iro'm4 1' to 12 1 respectively.

2. A lubricating composition comprising a major amount of liquidorganiclubricating base having incorporated therein from"0.01% to of a reaction product obtaine'dby reacting C2-C5 alkylene' oxide with an organic polyhydroxy carboxylic acid containing from -1 to 3 carboxylic acidgroups at a temperature of at least C. and in the mole ratio'of 4i1 to 2:1 respectively.

3. A lubricating composition comprising a, major amount of liquid organic lubricating base having incorporated therein'from-0;01'% tol0% of a reaction product obtained by reacting ethylene oxide with an organicp'olyhydroxy carboxylic acid containing froml' to 3 carboxylic acid-groups at a temperature of at least 75 C. and in the mole ratio of 4:1 to 2:1"respectively.

4. A lubricating composition comprising a major amount "of liquid organic lubricating base having incorporated therein from 0.01% to 10% of a reaction product obtained by reacting C2'-C5 alkylene oxide with an aliphatic polyhydroxy poly-carboxylidacid, said carboxylic acid radical being'not more than three in number, at a temperature of from 75 -C. to- 200.C. and in the mole ratio of 4:1 to 251 respectively.

5. A lubricating composition comprising a major amountof mineral oil having incorporated therein in an amount sufiicient to impart extreme pressure properties of a condensation reaction product obtained by reacting ethylene oxide and tartaric acid at a temperature of from '75 to C. in the mole ratio of about 10:1, respectively.

6. A lubricating composition comprising a major amount of mineral oil having incorporated therein in'an amount sufiicient to impart extreme pressure properties of a condensation reaction product obtained by reacting ethylene oxide and malic acid at a temperature of from 75 to 100 C. in the mole ratio of about 10:1, respectively.

7. A lubricating composition comprising a major amount of mineraloil having incorporated product obtained by reacting'ethylene sulfide and 13 tartaric acid at a temperature of from 75 to 100 C. in the mole ratio of about 10:1, respectively.

8. A lubricating composition comprising a major amount of a liquid organic lubricating base having incorporated therein from about 0.01 to 10% of a reaction product obtained by reacting an organic compound selected from the group consisting of C2-C5 alkylene oxide, C2-C5 alkylene sulfide, and C2-C5 alkylene imine with an organic poly acidic compound containing from 1 to 3 free carboxylic acid groups and at least one hydroxy group, said reaction being reacted at a temperature of at least 75 C. in the mole ratio of from 4:1 to 12:1 respectively and ire-treating about one mole of the reaction product thus formed with about four moles of a sulfurizing, sulfo-phosphorizing and phosphorizing agent at a temperature of at least 125 C.

9. A lubricating composition comprising a major amount of a liquid organic lubricating base having incorporated therein from about 0.01 to 10% of a reaction product obtained by reacting an organic compound selected from the group consisting of C2-C5 alkylene oxide, C2-C5 alkylone sulfide, and C2-C alkylene irnine with an organic poly acidic compound containing from 1 to 3 free carboxylic acid groups and at least one hydroxy group, said reaction being carried out at a temperature of at least 75 C. in the mole ratio of from 4: 1 to 12:1 respectively and treating about 1 mole of the condensation product thus formed with'about 4 moles of a sulfurizing agent at a temperature of around 160 C.

10. A lubricating composition comprising a major amount of a liquid organic lubricating base having incorporated therein from about 0.01 to of a reaction product obtained by reacting an organic compound selected from the group consisting of C2-C5 alkylene oxide, C2-C5 alkylene sulfide, and C2-C5 alkylene imine with an organic poly acidic compound containing from 1 to 3 free carboxylic acid groups and at least one hydroxy group, said reaction being carried out at a temperature of at least 75 C. in the mole ratio of from 4:1 to 12:1 respectively and treating about 1 mole of the condensation product thus formed with about 4 moles of a phosphorous sulfide at a temperature of around 250 C.

11. A lubricating composition comprising a major amount of a liquid organic lubricating base having incorporated therein from about 0.01 to 10% of a reaction product obtained by reacting a C2C5 alkylene oxide with an organic poly acidic compound containing from 1 to 3 carboxylic acid groups and at least one hydroxy group, said reaction being carried out at a temperature of at least C. in the mole ratio of from 4:1 to 12:1, respectively.

12. A lubricating composition comprising a. major amount of a liquid organic lubricating base having incorporated therein from about 0.01 to 10% of a reaction product obtained by reacting an ethylene oxide with-an organic poly acidic compound containing from 1 to 3 carboxylic acid groups and at least one hydroxy group, said reaction being carried out at a temperature of at least 75 C. in the mole ratio of from 4:1 to 12:1, respectively. f

DAVID E. ADELSON.

GEORGE L. PERRY.

GEORGE G. PRITZKER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,463,092 Pelly July 24, 1923 1,810,318 Loehr June 16, 1931 2,134,736 Reuter Nov. 1, 1938 2,341,846 Meincke Feb. 15, 1944 2,370,300 Farrington Feb. 27, 1945 2,457,139 Fife Dec. 28, 1948 2,481,278 Ballard Sept. 6, 1949 2,491,432 White Dec. 13, 1949 2,536,684 Harman et a1. Jan. 2, 1951 2,542,550 McDermott Feb. 20, 1951 

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF A LIQUID ORGANIC LUBRICATING BASE HAVING INCORPORATED THEREIN FROM ABOUT 0.01 TO 10% OF A REACTION PRODUCT OBTAINED BY REACTING AN ALIPHATIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF C2-C5 ALKYLENE OXIDE, C2-C5 ALKYLENE SULFIDE, AND C2-C5 ALKYLENE IMINE WITH AN ORGANIC POLY ACIDIC COMPOUND CONTAINING FROM 1 TO 3 FREE CARBOXYLIC ACID GROUPS AND AT LEAST ONE HYDROXY GROUP, SAID REACTION BEING CARRIED OUT AT A TEMPERATURE OF AT LEAST 75* C. IN THE MOLE RATIO OF FROM 4:1 TO 12:1 RESPECTIVELY. 